Mechanistic Studies on the Base-Promoted Conversion of Alkoxy-Substituted, Ring-Fused gem-Dihalocyclopropanes into Furans: Evidence for a Process Involving Electrocyclic Ring Closure of a Carbonyl Ylide Intermediate

Phillip P. Sharp, Jiri Mikusek, Junming Ho, Elizabeth H. Krenske, Martin G. Banwell, Michelle L. Coote, Jas S. Ward, Anthony C. Willis

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

The mechanism associated with the base-promoted conversion of alkoxy-substituted and ring-fused gem-dihalocyclopropanes such as 40 into annulated furans has been explored. Treatment of compound 40 with potassium tert-butoxide affords a mixture of furans 23/27 and 41, an outcome that suggests the intermediacy of the slowly interconverting carbonyl ylides 42 and 43 that undergo rapid [1,5]-electrocyclizations and subsequent dehydrohalogenation to afford the observed products. This proposal is supported by ab initio MO and DFT calculations that also suggest a vinylcarbene insertion pathway is less likely to be operative.

Original languageEnglish
Pages (from-to)13678-13690
Number of pages13
JournalJournal of Organic Chemistry
Volume83
Issue number22
DOIs
Publication statusPublished - 16 Nov 2018
Externally publishedYes

Keywords

  • Lipids
  • Chromatography
  • Chemical reactions
  • Organic compounds
  • Nuclear magnetic resonance spectroscopy

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